38112-60-6Relevant articles and documents
A One-Pot Synthesis of α,β-Unsaturated Esters From Esters
Hong, Chang Whee,Lee, Yong Jin,An, Duk Keun
, p. 1121 - 1125 (2021/06/01)
A convenient method for reductive Horner–Wadsworth–Emmons (HWE) olefination is described. The E-selective HWE homologation of various esters to α,β-unsaturated esters was readily achieved and gave the desired products in good-to-moderate yields under mild conditions. The one-pot reaction proceeds through an in situ generated aldehyde, formed via the partial reduction of an ester with lithium diisobutyl-t-butoxyaluminum hydride. The formation of cyclized metal acetal and subsequent decompose to the aldehyde for the olefination was found to be a crucial step in this C2-carbon homologation protocol.
Nickel-Catalyzed Decarboxylative Alkenylation of Anhydrides with Vinyl Triflates or Halides
Chen, Hui,Sun, Shuhao,Liao, Xuebin
supporting information, p. 3625 - 3630 (2019/05/24)
Decarboxylative cross-coupling of aliphatic acid anhydrides with vinyl triflates or halides was accomplished via nickel catalysis. This methodology works well with a broad array of substrates and features abundant functional group tolerance. Notably, our approach addresses the issue of safe and environmental installation of methyl or ethyl group into molecular scaffolds. The method possesses high chemoselectivity toward alkyl groups when aliphatic/aromatic mixed anhydrides are involved. Furthermore, diverse ketones could be modified with our strategy.
Synthesis of α,β-unsaturated aldehydes as potential substrates for bacterial luciferases
Brodl, Eveline,Ivkovic, Jakov,Tabib, Chaitanya R.,Breinbauer, Rolf,Macheroux, Peter
, p. 1487 - 1495 (2017/02/18)
Bacterial luciferase catalyzes the monooxygenation of long-chain aldehydes such as tetradecanal to the corresponding acid accompanied by light emission with a maximum at 490?nm. In this study even numbered aldehydes with eight, ten, twelve and fourteen carbon atoms were compared with analogs having a double bond at the α,β-position. These α,β-unsaturated aldehydes were synthesized in three steps and were examined as potential substrates in vitro. The luciferase of Photobacterium leiognathi was found to convert these analogs and showed a reduced but significant bioluminescence activity compared to tetradecanal. This study showed the trend that aldehydes, both saturated and unsaturated, with longer chain lengths had higher activity in terms of bioluminescence than shorter chain lengths. The maximal light intensity of (E)-tetradec-2-enal was approximately half with luciferase of P. leiognathi, compared to tetradecanal. Luciferases of Vibrio harveyi and Aliivibrio fisheri accepted these newly synthesized substrates but light emission dropped drastically compared to saturated aldehydes. The onset and the decay rate of bioluminescence were much slower, when using unsaturated substrates, indicating a kinetic effect. As a result the duration of the light emission is doubled. These results suggest that the substrate scope of bacterial luciferases is broader than previously reported.
